The present invention relates to certain novel naphthopyran compounds. More particularly, this invention relates to novel indeno-fused photochromic naphthopyran compounds and to compositions and articles containing such novel naphthopyran compounds. When exposed to light radiation containing ultraviolet rays, such as the ultraviolet radiation in sunlight or the light of a mercury lamp, many photochromic compounds exhibit a reversible change in color. When the ultraviolet radiation is discontinued, such a photochromic compound will return to its original color or colorless state.
Various classes of photochromic compounds have been synthesized and suggested for use in applications in which a sunlight-induced reversible color change or darkening is desired. U.S. Pat. No. 3,567,605 (Becker) describes a series of pyran derivatives, including certain benzopyrans and naphthopyrans. These compounds are described as derivatives of chromene and are reported to undergo a color change, e.g., from colorless to yellow-orange, on irradiation by ultraviolet light at temperatures below about xe2x88x9230xc2x0 C. Irradiation of the compounds with visible light or upon raising the temperature to above about 0xc2x0 C. is reported to reverse the coloration to a colorless state.
U.S. Pat. No. 5,066,818 describes various 3,3-diaryl-3H-naphtho[2,1-b]pyrans as having desirable photochromic properties, i.e., high colorability and acceptable fade, for ophthalmic and other applications. Also disclosed by way of comparative example in the ""818 patent are the isomeric 2,2-diaryl-2H-naphtho[1,2-b]pyrans, which are reported to require unacceptably long periods of time to fade after activation.
U.S. Pat. No. 3,627,690 describes photochromic 2,2-di-substituted-2H-naphtho[1,2-b]pyran compositions containing minor amounts of either a base or weak-to-moderate strength acid. The addition of either an acid or base to the naphthopyran composition is reported to increase the fade rate of the colored naphthopyrans, thereby making them useful in eye protection applications such as sunglasses. It is reported therein further that the fade rate of 2H-naphtho-[1,2-b]pyrans without the aforementioned additives ranges from several hours to many days to reach complete reversion.
Indenonaphthopyrans are known and have been disclosed in U.S. Pat. Nos. 5,645,767, 5,698,141, 5,723,072, 6,113,814 and 6,146,554 and International Patent Application Publication No. WO 99/15518. In each of these disclosures, the indeno group is in a reversed position as compared to the indenonaphthopyrans of the present invention. Japan Unexamined Patent Publication P2000-327675A discloses an indenonaphthopyran in which the indeno group is substituted with fluorenyl.
The present invention relates to a naphthopyran of 2H-naphtho[1,2-b]pyran structure characterized by having a substituted or unsubstituted indeno group fused at the 2,3 positions of the group to the 1 side of the naphthopyran. The compounds also have substituents at the 3 position of the pyran ring. These compounds have unexpectedly been found to demonstrate a bathochromic shift for the wavelength in the visible spectrum at which the maximum absorption of the activated (colored) form of the photochromic compound, i.e., the lambda max (Vis), occurs, thereby resulting in activated colors ranging from yellow/brown to blue/gray. Due to the bathochromic shift, compounds of the present invention demonstrate different colors than similar compounds without an unsubstituted or substituted indeno group fused at the 2,3 position of the group to the 1 side of the napthopyran. In addition, compounds of the present invention have demonstrated a high molar absorptivity (or molar extinction coefficient) in the UV, an acceptable fade rate without the addition of acids or bases, a high activated intensity, and a high coloration rate.
In recent years, photochromic plastic materials, particularly plastic materials for optical applications, have been the subject of considerable attention. In particular, photochromic ophthalmic plastic lenses have been investigated because of the weight advantage they offer, vis-a-vis, glass lenses. Moreover, photochromic transparencies for vehicles, such as cars and airplanes, have been of interest because of the potential safety features that such transparencies offer.
Other than in the operating examples, or where otherwise indicated, all values, such as those expressing wavelengths, quantities of ingredients, ranges or reaction conditions, used in this description and the accompanying claims are understood as modified in all instances by the term xe2x80x9caboutxe2x80x9d which means close to or near.
As used herein, the terms xe2x80x9chaloxe2x80x9d and xe2x80x9chalogenxe2x80x9d are defined to include chloro, fluoro, bromo and iodo and chlorine, fluorine, bromine and iodine, respectively. The term xe2x80x9carylxe2x80x9d is defined herein to include phenyl and naphthyl.
The disclosures of the patents and articles cited herein describing photochromic imbibition processes and compositions, procedures for making polymerizable and nonpolymerizable compounds of the present invention, complementary photochromic compounds, polymeric coatings and methods of applying such coatings, polymeric organic host materials and polymerizates are incorporated herein, in toto, by reference.
In accordance with the present invention, it has now been discovered that novel 2H-naphtho[1,2-b]pyran structures characterized by having a substituted or unsubstituted indeno group fused at the 2,3 positions of the group to the 1 side of the naphthopyran and demonstrating activated colors ranging from yellow/brown to blue/gray, an acceptable fade rate, high activated intensity and a high coloration rate may be prepared. These compounds may be described as indeno[3xe2x80x2,2xe2x80x2:3,4]naphtho[1,2-b]pyrans having substituents at the 3 position of the pyran ring. Substituents may also be present at the number 5, 6, 7, 8, 9, 10, 11, 12, or 13 carbon atoms of the compounds. The indeno group may be represented by the following graphic formula Ixe2x80x2 in which numbers 1 through 9 represent the ring atoms of the indeno group. 
A typical 2H-naphtho[1,2-b]pyran structure is represented by the following graphic formula Ixe2x80x3, in which the letters a through n represent the sides and X represents potential substituents known in the art. 
The compounds of the present invention may be represented by the following graphic formula I in which the letters a through u represent the sides of the indenonaphthopyran rings, and the numbers represent the numbers of the ring atoms of the indenonaphthopyran. 
The indenonaphthopyran of the present invention is a naphthopyran compound of 2H-naphtho[1,2-b]pyran structure, such as represented by graphic formula Ixe2x80x3, characterized by having fused to the 1 side of the 2H-naphthopyran a group represented by graphic formula Ixe2x80x2 at the 2,3 positions of group Ixe2x80x2. The group represented by graphic formula Ixe2x80x2 may be unsubstituted such as when R1 and R2 are each hydrogen and equals 0 or may be substituted with substituents known in the art for use on photochromic compounds. Different embodiments of the compounds of the present invention are contemplated based on photochromic activity.
In graphic formulae Ixe2x80x2, R1 and R2 may each be selected from the group consisting of:
(i) hydrogen, hydroxy, amino, mono- and di-substituted amino, C1-C6 alkyl, C1-C6 haloalkyl, C3-C7 cycloalkyl, allyl, benzyl, mono-substituted benzyl, halogen and the group, xe2x80x94C(O)W, wherein W is hydroxy, C1-C6 alkyl, C1-C6 alkoxy, C3-C7 cycloalkyloxy, phenyl, mono-substituted phenyl, phenoxy, amino, mono(C1-C6)alkylamino, di(C1-C6)alkylamino, morpholino, piperidino or pyrrolidyl, said amino substituents being selected from the group consisting of C1-C6 alkyl, phenyl, benzyl and naphthyl, said benzyl and phenyl substituents being C1-C6 alkyl, C1-C6 alkoxy, piperidino, morpholino, di(C1-C6)alkylamino or fluoro;
(ii) unsubstituted, mono- di- and tri-substituted members selected from the group consisting of phenyl, naphthyl, phenanthryl, pyrenyl, quinolyl, isoquinolyl, benzofuranyl, thienyl, benzothienyl, dibenzofuranyl, dibenzothienyl, carbazolyl, and indolyl, said group substituents being selected from the group consisting of halogen, C1-C6 alkyl, C1-C6 alkoxy, morpholino, piperidino, pyrrolidino, amino, mono- and di-substituted amino, said amino substituents being selected from the group consisting of C1-C6 alkyl, phenyl, benzyl and naphthyl;
(iii) monosubstituted phenyl, having a substituent at the para position that is a linking group, xe2x80x94(CH2)txe2x80x94 or xe2x80x94Oxe2x80x94(CH2)txe2x80x94, wherein t is the integer 1, 2, 3, 4, 5 or 6, connected to an aryl group, which is a member of another photochromic naphthopyran;
(iv) a group, xe2x80x94OR5, wherein R5 is C1-C6 alkyl, C1-C6 acyl, phenyl(C1-C3)alkyl, mono(C1-C6)alkyl substituted phenyl(C1-C3)alkyl, mono(C1-C6)alkoxy substituted phenyl(C1-C3)alkyl, C1-C6 alkoxy(C2-C4)alkyl, C3-C7 cycloalkyl, mono(C1-C4)alkyl substituted C3-C7 cycloalkyl, C1-C6 haloalkyl, allyl, benzoyl, monosubstituted benzoyl, naphthoyl or monosubstituted naphthoyl, said benzoyl and naphthoyl group substituents being C1-C6 alkyl or C1-C6 alkoxy; or R5 is the group xe2x80x94CH(R6)Q, wherein R6 is hydrogen or C1-C3 alkyl and Q is xe2x80x94CN, xe2x80x94CF3, or xe2x80x94COOR7, and R7 is hydrogen or C1-C3 alkyl; or R5 is the group, xe2x80x94C(O)V, wherein V is hydrogen, C1-C6 alkoxy, phenoxy, mono- or di-(C1-C6)alkyl substituted phenoxy, mono- or di-(C1-C6)alkoxy substituted phenoxy, an unsubstituted, mono- or di-substituted aryl group, amino, mono(C1-C6)alkylamino, di(C1-C6)alkylamino, phenylamino, mono- or di-(C1-C6)alkyl substituted phenylamino, or mono- or di-(C1-C6)alkoxy substituted phenylamino, said aryl group substituents being C1-C6 alkyl or C1-C6 alkoxy;
(v) a group, xe2x80x94CH(Qxe2x80x2)2, wherein Qxe2x80x2 is xe2x80x94CN or xe2x80x94COOR8, wherein R8 is hydrogen, C1-C6 alkyl, phenyl(C1-C3)alkyl, mono(C1-C6)alkyl substituted phenyl(C1-C3)alkyl, mono(C1-C6)alkoxy substituted phenyl(C1-C3)alkyl, or an unsubstituted, mono- or di-substituted aryl group, each of said aryl group substituents being C1-C6 alkyl or C1-C6 alkoxy;
(vi) a group, xe2x80x94CH(R9)G, wherein R9 is hydrogen, C1-C6 alkyl or an unsubstituted, mono- or di-substituted aryl group, and G is hydroxy, C1-C6 alkoxy, aryloxy, amino, mono(C1-C6)alkylamino, di(C1-C6)alkylamino, phenylamino, mono- or di-(C1-C6)alkyl substituted phenylamino, or mono- or di-(C1-C6)alkoxy substituted phenylamino, xe2x80x94COOR8, xe2x80x94COR10 or xe2x80x94CH2OR11, wherein R10 is hydrogen, C1-C6 alkyl, an unsubstituted, mono- or di-substituted aryl group, amino, mono(C1-C6)alkylamino, di(C1-C6)alkylamino, phenylamino, mono- or di-(C1-C6)alkyl substituted phenylamino, mono- or di-(C1-C6)alkoxy substituted phenylamino, diphenylamino, mono- or di(C1-C6)alkyl substituted diphenylamino, mono- or di(C1-C6)alkoxy substituted diphenylamino, morpholino, or piperidino, wherein R11 is hydrogen, xe2x80x94C(O)R8, C1-C6 alkyl, C1-C3 alkoxy(C1-C6)alkyl, phenyl(C1-C3)alkyl, mono(C1-C6)alkoxy substituted phenyl(C1-C3)alkyl, or an unsubstituted, mono- or di-substituted aryl group, each of said aryl group substituents being C1-C6 alkyl or C1-C6 alkoxy; and
(vii) a group, T, represented by the formula:
xe2x80x94Z[(OC2H4)x(OC3H6)y(OC4H8)z]Zxe2x80x2
xe2x80x83or
xe2x80x94[(OC2H4)x(OC3H6)y(OC4H8)z]Zxe2x80x2
xe2x80x83wherein xe2x80x94Z is xe2x80x94C(O)xe2x80x94 or xe2x80x94CH2xe2x80x94, Zxe2x80x2 is C1-C3 alkoxy or a polymerizable group i.e., any functional group capable of participating in a polymerization reaction. Polymer forming methods in which the polymerizable compounds of the present invention may participate include radical polymerization, and such other polymerization processes as are described in Ullmann""s Encyclopedia of Industrial Chemistry, xe2x80x9cPolymerization Processesxe2x80x9d, Vol. 21A, pp 305 to 428. The polymerizable groups may be selected from the group consisting of hydroxy, (meth)acryloxy, vinyl, isocyanate and epoxy, e.g., oxiranylmethyl. When there are 2 or more polymerizable groups on the naphthopyran, they may be the same or different, x, y and z are each a number between 0 and 50, and the sum of x, y and z is between 2 and 50; or
(viii) R1 and R2 may together form a substituted or unsubstituted spiro-carbocyclic ring containing 3 to 6 carbon atoms or a substituted or unsubstituted spiro-heterocyclic group containing 1 or 2 oxygen atoms and 3 to 6 carbon atoms including the spirocarbon atom, said spiro-carbocyclic ring and spiro-heterocyclic group being annellated with 0, 1 or 2 benzene rings, said substituents being hydrogen or C1-C6 alkyl, provided that said spiro-carbocyclic ring is not fluoren-9-ylidene.
In one contemplated embodiment, R1 and R2 are each selected from the group consisting of:
(i) hydrogen, hydroxy, C1-C6 alkyl, C1-C6 haloalkyl, di-substituted amino, C3-C7 cycloalkyl, benzyl, mono-substituted benzyl and the group, xe2x80x94C(O)W, wherein W is C1-C6 alkoxy, di(C1-C6)alkylamino, morpholino or piperidino, said amino substituents being C1-C6 alkyl, said benzyl substituents being C1-C6 alkyl or C1-C6 alkoxy;
(ii) mono- and di and tri-substituted members selected from the group consisting of phenyl, naphthyl and dibenzofuranyl, said group substituents being selected from the group consisting of C1-C6 alkyl, C1-C6 alkoxy, and di-substituted amino, said amino substituents being C1-C6 alkyl;
(iii) monosubstituted phenyl, having a substituent at the para position that is a linking group, xe2x80x94Oxe2x80x94(CH2)txe2x80x94, wherein t is the integer 3, 4 or 5 connected to an aryl group, which is a member of another photochromic naphthopyran;
(iv) a group, xe2x80x94OR5, wherein R5 is C1-C6 alkyl, C1-C6 acyl, C1-C6 alkoxy (C2-C4) alkyl, benzoyl or monosubstituted benzoyl, said benzoyl substituents being C1-C6 alkyl or C1-C6 alkoxy; or R5 is the group xe2x80x94CH(R6)Q, wherein R6 is hydrogen and Q is xe2x80x94COOR7, and R7 is C1-C3 alkyl; or R5 is the group, xe2x80x94C(O)V, wherein V is C1-C6 alkoxy or di(C1-C6)alkyl amino;
(v) a group, xe2x80x94CH(Qxe2x80x2)2, wherein Qxe2x80x2 is xe2x80x94COOR8, wherein R8 is C1-C6 alkyl, or phenyl(C1-C3)alkyl;
(vi) a group, xe2x80x94CH(R9)G, wherein R9 is C1-C6 alkyl, and G is C1-C6 alkoxy, xe2x80x94COOR8xe2x80x94COR10, or xe2x80x94CH2OR11, wherein R10 is C1-C6 alkyl, di(C1-C6)alkylamino, morpholino or piperidino; wherein R11 is C1-C6 alkyl or C1-C3 alkoxy(C1-C6) alkyl, and
(vii) a group, T, represented by the formula:
[(OC2H4)x(OC3H6)y(OC4H8)z]Zxe2x80x2
xe2x80x83wherein Zxe2x80x2 is C1-C3 alkoxy or a polymerizable group, x, y and z are each a number between 0 and 50, and the sum of x, y and z is between 2 and 50; or
(viii) R1 and R2 may together form an oxo group or a substituted or unsubstituted spiro-heterocyclic group containing 1 or 2 oxygen atoms and 3 to 6 carbon atoms including the spirocarbon atom, said spiro-heterocyclic ring being annellated with 1 or 2 benzene rings, said substituent being C1-C6 alkyl.
In another contemplated embodiment, R1 and R2 are each selected from the group consisting of:
(i) hydrogen, hydroxy, C1-C3 alkyl and the group, xe2x80x94C(O)W, wherein W is C1-C6 alkoxy,;
(ii) unsubstituted, and mono-substituted phenyl, said phenyl substituents being selected from the group consisting of C1-C6 alkoxy, and di-substituted amino, said amino substituents being C1-C3 alkyl;
(iii) monosubstituted phenyl, having a substituent at the para position that is a linking group, xe2x80x94Oxe2x80x94(CH2)txe2x80x94, wherein t is the integer 3, connected to an aryl group, which is a member of another photochromic naphthopyran;
(iv) a group, xe2x80x94OR5, wherein R5 is C1-C6 alkyl, C1-C6 alkoxy(C2-C4)alkyl, the group xe2x80x94CH(R6)Q, wherein R6 is hydrogen or C1-C3 alkyl and Q is xe2x80x94COOR7, and R7 is C1-C3 alkyl or R5 is the group, xe2x80x94C(O)V, wherein V is C1-C6 alkoxy;
(v) a group, xe2x80x94CH(Qxe2x80x2)2, wherein Qxe2x80x2 is xe2x80x94COOR8, wherein R8 is C1-C6 alkyl;
(vi) a group, xe2x80x94CH(R9)G, wherein R9 is C1-C6 alkyl, and G is C1-C6 alkoxy, xe2x80x94COOR8, xe2x80x94COR10 or xe2x80x94CH2OR11 wherein R10 and R11 are each C1-C6 alkyl; and
(vii) a group, T, represented by the formula:
xe2x80x94[(OC2H4)x(OC3H6)y(OC4H8)z]Zxe2x80x2
xe2x80x83wherein Zxe2x80x2 is C1-C3 alkoxy or a polymerizable group, x, y and z are each a number between 0 and 50, and the sum of x, y and z is between 2 and 50; or
(viii) R1 and R2 may together form a substituted or unsubstituted spiro-heterocyclic group containing 1 oxygen atom and 6 carbon atoms including the spirocarbon atom, said spiro-heterocyclic ring being annellated with 2 benzene rings, said substituents being C1-C3 alkyl.
R3 may be selected from the group of substituents known in the art for use on photochromic compounds. Each R3 in graphic formula I may independently be selected from the group consisting of hydrogen, C1-C6 alkyl, C1-C6 alkoxy, C3-C7 cycloalkyl, phenyl, benzyl, di(C1-C6)alkylamino, dicyclohexylamino, diphenylamino, piperidyl, morpholinyl, pyridyl, halogen, a group, T, and the group xe2x80x94C(O)W and n is the integer 0, 1, or 2; or when n is at least 2, and the R3 substituents are adjacent, the pair of substituents forms a substituted or unsubstituted fused carbocyclic or heterocyclic ring selected from the group consisting of benzo, pyridino, pyrazino, pyrimidino, furano, dihydrofurano, 1,3-dioxolo, 1,4-dioxolo, 1,3-dioxino, 1,4-dioxino, thiopheno, benzofuro, benzothieno, indolo, and indeno, the substituents of said fused carbocyclic or heterocyclic ring being selected from the group consisting of halogen, C1-C6 alkyl, C1-C6 alkoxy, amino, mono- and di-substituted amino, said amino substituents being selected from the group consisting of C1-C6 alkyl, phenyl, benzyl and naphthyl; said first R3 ring being fused to the o, p or q side and said second R3 ring being fused to the g, h, or i side of the naphthopyran.
In one contemplated embodiment, each R3 is selected from the group consisting of hydrogen, C1-C6 alkyl, C1-C6 alkoxy, di(C1-C6)alkylamino, piperidyl, morpholinyl, pyrrolidyl, halogen, a group, T, or the group, xe2x80x94C(O)W and n is the integer 0, 1, or 2; or when n is 2, and the R3 substituents are adjacent, a pair of substituents forms a substituted or unsubstituted fused carbocyclic or heterocyclic ring selected from the group consisting of benzo, dihydrofurano and benzofuro, the substituents of said fused carbocyclic or heterocyclic ring being selected from the group consisting of C1-C6 alkyl, C1-C6 alkoxy, and di-substituted amino, said amino substituents being C1-C6 alkyl; said R3 ring being fused to the o, p or q sides of the naphthopyran.
In another contemplated embodiment, each R3 is selected from the group consisting of hydrogen C1-C6 alkyl, C1-C6 alkoxy, morpholinyl, a group, T, and the group xe2x80x94C(O)W, and when m is 2 and the R3 substituents are adjacent, the pair of substituents forms a substituted or unsubstituted fused carbocyclic or heterocyclic ring selected from the group consisting of benzo and benzofuro, the substituents of said fused carbocyclic or heterocyclic ring being C1-C6 alkoxy; said R3 ring being fused to the p side of the naphthopyran.
In graphic formula I, R1, R2 and each R3 are the same as described hereinbefore for graphic formula Ixe2x80x2. In the definitions of R1, R2, R3, B and Bxe2x80x2, like substituents have like meanings.
B and Bxe2x80x2 in graphic formula I may each be selected from the group of substituents known in the art for use on photochromic compounds. Specifically, B and Bxe2x80x2 may each be selected from the group consisting of:
(i) mono-T-substituted phenyl
(ii) an unsubstituted, mono-, di-, and tri-substituted aryl group;
(iii) 9-julolidinyl and an unsubstituted, mono- or di-substituted heteroaromatic group selected from the group consisting of pyridyl, furanyl, benzofuran-2-yl, benzofuran-3-yl, thienyl, benzothien-2-yl, benzothien-3-yl, dibenzofuranyl, dibenzothienyl, carbazoyl, benzopyridyl, indolinyl and fluorenyl, each of said aryl and heteroaromatic substituents in (ii) and (iii) being selected from the group consisting of hydroxy, aryl, i.e., phenyl and naphthyl, mono(C1-C6)alkoxyaryl, di(C1-C6)alkoxyaryl, mono(C1-C6)alkylaryl, di(C1-C6)alkylaryl, haloaryl, C3-C7 cycloalkylaryl, C3-C7 cycloalkyl, C3-C7 cycloalkyloxy, C3-C7 cycloalkyloxy(C1-C6)alkyl, C3-C7 cycloalkyloxy(C1-C6)alkoxy, aryl(C1-C6)alkyl, aryl(C1-C6)alkoxy, aryloxy, aryloxy(C1-C6)alkyl, aryloxy(C1-C6)alkoxy, mono- and di-(C1-C6)alkylaryl(C1-C6)alkyl, mono- and di-(C1-C6)alkoxyaryl(C1-C6)alkyl, mono- and di-(C1-C6)alkylaryl(C1-C6)alkoxy, mono- and di-(C1-C6)alkoxyaryl(C1-C6)alkoxy, amino, mono(C1-C6)alkylamino, di(C1-C6)alkylamino, diarylamino, aryl(C1-C6 alkyl)amino, piperazino, N-(C1-C6)alkylpiperazino, N-arylpiperazino, aziridino, indolino, piperidino, morpholino, thiomorpholino, tetrahydroquinolino, tetrahydroisoquinolino, pyrryl, pyrrolidyl, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, mono(C1-C6)alkoxy(C1-C4)alkyl, acryloxy, methacryloxy and halogen;
(iv) an unsubstituted or mono-substituted member selected from the group consisting of pyrazolyl, imidazolyl, pyrazolinyl, imidazolinyl, pyrrolinyl, phenothiazinyl, phenoxazinyl, phenazinyl and acridinyl, each of said substituents being selected from the group consisting of C1-C6 alkyl, C1-C6 alkoxy, phenyl, and halogen;
(v) monosubstituted phenyl, having a substituent at the para position that is a linking group, xe2x80x94(CH2)txe2x80x94 or xe2x80x94Oxe2x80x94(CH2)txe2x80x94, wherein t is the integer 1, 2, 3, 4, 5 or 6, connected to an aryl group, which is a member of another photochromic naphthopyran;
(vi) a group represented by one of the following graphic formula IIA or IIB: 
xe2x80x83wherein A is methylene or oxygen and D is oxygen or substituted nitrogen, provided that when D is substituted nitrogen, A is methylene, said nitrogen substituents being selected from the group consisting of hydrogen, C1-C6 alkyl, and C2-C6 acyl; each R12 is C1-C6 alkyl, C1-C6 alkoxy, hydroxy, or halogen; R13 and R14 are each hydrogen or C1-C6 alkyl; and q is the integer 0, 1, or 2;
(vii) C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy(C1-C4)alkyl, C3-C6 cycloalkyl, mono(C1-C6)alkoxy(C3-C6)cycloalkyl, mono(C1-C6)alkyl(C3-C6)cycloalkyl, halo(C3-C6)cycloalkyl, and C4-C12 bicycloalkyl; and
(viii) a group represented by the following graphic formula IIC: 
xe2x80x83wherein L is hydrogen or C1-C4 alkyl and M is selected from the unsubstituted, mono-, and di-substituted members of the group consisting of naphthyl, phenyl, furanyl, and thienyl, each of said group substituents being C1-C4 alkyl, C1-C4 alkoxy, or halogen.
Alternatively, B and Bxe2x80x2 may together form fluoren-9-ylidene, mono-, or di-substituted fluoren-9-ylidene or form a member selected from the group consisting of saturated C3-C12 spiro-monocyclic hydrocarbon rings, e.g., cyclopropylidene, cyclobutylidene, cyclopentylidene, cyclohexylidene, cycloheptylidene, cyclooctylidene, cyclononylidene, cyclodecylidene cycloundecylidene, cyclododecylidene; saturated C7-C12 spiro-bicyclic hydrocarbon rings, e.g., bicyclo[2.2.1]heptylidene, i.e., norbornylidene, 1,7,7-trimethyl bicyclo[2.2.1]heptylidene, i.e., bornylidene, bicyclo[3.2.1]octylidene, bicyclo[3.3.1]nonan-9-ylidene, bicyclo[4.3.2]undecane, and saturated C7-C12 spiro-tricyclic hydrocarbon rings, e.g., tricyclo[2.2.1.02,6]heptylidene, tricyclo[3.3.1.13,7]decylidene, i.e., adamantylidene, and tricyclo[5.3.1.12,6]dodecylidene, each of said fluoren-9-ylidene substituents being selected from the group consisting of C1-C4 alkyl, C1-C4 alkoxy, and halogen.
In one contemplated embodiment, B and Bxe2x80x2 are each selected from the group consisting of: (i) phenyl, mono-substituted phenyl, and di-substituted phenyl, preferably substituted in the meta and/or para positions; (ii) the unsubstituted, mono- and di-substituted aromatic heterocyclic groups furanyl, benzofuran-2-yl, thienyl, benzothien-2-yl and dibenzofuranyl, each of said phenyl and aromatic heterocyclic substituents being selected from the group consisting of hydroxy, amino, mono(C1-C3)alkylamino, di(C1-C3)alkylamino, piperidino, morpholino, pyrryl, C1-C3 alkyl, C1-C3 chloroalkyl, C1-C3 fluoroalkyl, C1-C3 alkoxy, mono(C1-C3)alkoxy(C1-C3)alkyl, fluoro and chloro; (iii) the groups represented by the graphic formulae IIA and IIB, wherein A is methylene and D is oxygen, R12 is C1-C3 alkyl or C1-C3 alkoxy, R13 and R14 are each hydrogen or C1-C4 alkyl; and q is the integer 0 or 1; (iv) C1-C4 alkyl; and (v) the group represented by the graphic formula IIC wherein L is hydrogen or methyl and M is phenyl or mono-substituted phenyl, said phenyl substituent being selected from the group consisting of C1-C3 alkyl, C1-C3 alkoxy, and fluoro; or (vi) B and Bxe2x80x2 taken together form fluoren-9-ylidene, mono-substituted fluoren-9-ylidene or a member selected from the group consisting of saturated C3-C8 spiro-monocyclic hydrocarbon rings, saturated C7-C10 spiro-bicyclic hydrocarbon rings, and saturated C7-C10 spiro-tricyclic hydrocarbon rings, said fluoren-9-ylidene substituent being selected from the group consisting of C1-C3 alkyl, C1-C3 alkoxy, fluoro and chloro.
In another contemplated embodiment, B and Bxe2x80x2 are each selected from the group consisting of (i) phenyl, mono- and di-substituted phenyl, (ii) the unsubstituted, mono- and di-substituted aromatic heterocyclic groups furanyl, benzofuran-2-yl, thienyl, benzothien-2-yl and dibenzofuranyl, each of said phenyl and aromatic heterocyclic substituents being selected from the group consisting of hydroxy, C1-C3 alkyl, C1-C3 alkoxy, piperidino and morpholino; and (iii) the group represented by graphic formula IIA, wherein A is methylene and D is oxygen, R12 is C1-C3 alkyl or C1-C3 alkoxy, R13 and R14 are each hydrogen or C1-C3 alkyl, and q is the integer 0 or 1; or (iv) B and Bxe2x80x2 taken together form fluoren-9-ylidene, adamantylidene, bornylidene, norbornylidene, or bicyclo[3.3.1]nonan-9-ylidene.
Compounds represented by graphic formula I having certain of the substituents R1-R3, B and Bxe2x80x2 described hereinbefore, may be prepared by the following Reactions A through G. Methods for the preparation of compounds wherein R1, R2, B and/or Bxe2x80x2 is the polyalkoxylated group T are described in U.S. Pat. No. 5,961,892. Methods for the preparation of compounds wherein R1, R2, B and/or Bxe2x80x2 is the polymerizable polyalkoxylated group T are described in U.S. Pat. No. 6,113,814.
With reference to the following reactions, compounds represented by graphic formula V or VA are either purchased or prepared by Friedel-Crafts methods shown in Reaction A using an appropriately substituted or unsubstituted benzoyl chloride of graphic formula IV with a commercially available substituted or unsubstituted benzene compound of graphic formula III. See the publication Friedel-Crafts and Related Reactions, George A. Olah, Interscience Publishers, 1964, Vol. 3, Chapter XXXI (Aromatic Ketone Synthesis), and xe2x80x9cRegioselective Friedel-Crafts Acylation of 1,2,3,4-Tetrahydroquinoline and Related Nitrogen Heterocycles: Effect on NH Protective Groups and Ring Sizexe2x80x9d by Ishihara, Yugi et al, J. Chem. Soc., Perkin Trans. 1, pages 3401 to 3406, 1992.
In Reaction A, the compounds represented by graphic formulae III and IV are dissolved in a solvent, such as carbon disulfide or methylene chloride, and reacted in the presence of a Lewis acid, such as aluminum chloride or tin tetrachloride, to form the corresponding substituted benzophenone represented by graphic formula V (VA in Reaction B). R and Rxe2x80x2 represent possible substituents, as described hereinbefore with respect to B and Bxe2x80x2 of graphic formula I. 
In Reaction B, the substituted or unsubstituted ketone represented by graphic formula VA, in which B and Bxe2x80x2 may represent groups other than substituted or unsubstituted phenyl, as shown in graphic formula V, is reacted with sodium acetylide in a suitable solvent, such as anhydrous tetrahydrofuran (THF), to form the corresponding propargyl alcohol represented by graphic formula VI. Propargyl alcohols having B or Bxe2x80x2 groups other than substituted and unsubstituted phenyl may be prepared from commercially available ketones or ketones prepared via reaction of an acyl halide with a substituted or unsubstituted benzene, naphthalene or heteroaromatic compound, e.g., 9-julolidinyl. Propargyl alcohols having a B or Bxe2x80x2 group represented by graphic formula IIC may be prepared by the methods described in U.S. Pat. No. 5,274,132, column 2, lines 40 to 68. 
In Reaction C, a substituted or unsubstituted xcex1-methoxy naphthalene represented by graphic formula VII is reacted with a benzoyl chloride (IV) in the presence of anhydrous aluminum chloride to form a naphthophenone represented by graphic formula VIII. Compound VIII is reacted with an organometallic compound containing R1 to give a carbinol compound represented by graphic formula IX. Compound IX is heated with phosphoric acid to produce the ketone represented by graphic formula X. Compound X is aromatized by reaction with a base such as KOH in a water/ethanol mixture to produce the indeno-fused naphthol of graphic formula XI. 
In Reaction D, an ortho bromo acetophenone represented by graphic formula XII is reacted with ethyl, xcex1-benzoylacetate represented by graphic formula XIII in the presence of sodium hydride and cuprous bromide to form a naphthol represented by graphic formula XIV. Naphthol XIV is then hydrolyzed with aqueous base followed by cyclization in strong acid such as phosphoric acid to produce the indeno-fused naphthol represented by graphic formula XV. 
In Reaction E, the naphthol represented by graphic formula XI is coupled with a propragyl alcohol (VI) in the presence of a catalytic amount of a acid such as p-dodecylbenzene sulfonic acid to form an indenonaphthopyran represented by graphic formula IA. Compound IA is reacted with a strong base such as butyl lithium or KOH and followed by reaction with alkyl halide to produce the indenonaphthopyran represented by graphic formula IB. 
In Reaction F, the naphthol represented by graphic formula XV is coupled with propargyl alcohol to give the indenonaphthopyran represented by graphic formula XVI. Compound XVI is reacted with an organo metallic compound to produce the indenonaphthopyran of graphic formula IC. The hydroxy group on compound IC is alkylated with alcohol to form an ether substituent on the indenonaphthopyran of graphic formula ID. 
In Reaction G, the ortho bromoacetophenone represented by graphic formula XII is reacted with diethyl malonate represented by graphic formula XVII in the presence of sodium hydride and cuprous bromide to form a dihydroxy naphthalene represented by graphic formula XVIII. Compound XVIII is coupled with a propargyl alcohol (VI) to produce the naphthopyran represented by graphic formula IXX. Compound IXX is methylated with methyl iodide in the presence of potassium carbonate to form the naphthopyran represented by graphic formula XX. The reaction of the aryl Grignard reagent represented by graphic formula XXI with compound XX produces the naphthopyran represented by graphic formula XXII. Compound XXII is reacted with alkyl lithium to produce a carbinol derivative represented by graphic formula XXIII. Cyclization of Compound XXIII with acid forms the desired indenonaphthopyran represented by graphic formula IE. 
Compounds represented by graphic formula I may be used in those applications in which organic photochromic substances may be employed, such as optical lenses, e.g., vision correcting ophthalmic lenses, contact lenses and plano lenses, face shields, goggles, visors, camera lenses, windows, automotive windshields, aircraft and automotive transparencies, e.g., T-roofs, sidelights and backlights, plastic films and sheets, textiles and coatings, e.g., coating compositions As used herein, coating compositions are defined herein to include polymeric coating compositions prepared from materials such as polyurethanes, epoxy resins and other resins used to produce synthetic polymers; paints, i.e., a pigmented liquid or paste used for the decoration, protection and/or the identification of a substrate; and inks, i.e., a pigmented liquid or paste used for writing and printing on substrates. Potential substrates for coating compositions containing the compounds of the present invention include paper, glass, ceramics, wood, masonry, textiles, metals and polymeric organic materials.
Coating compositions may be used to produce coatings on optical elements, verification marks on security documents, e.g., documents such as banknotes, passport and drivers"" licenses, for which authentication or verification of authenticity may be desired. The indenonaphthopyrans represented by graphic formula I exhibit color changes from colorless to colors ranging from yellow/brown to blue/gray.
Examples of indenonaphthopyran compounds within the scope of the invention are the following:
(a) 3,3,9-triphenyl-3H-9H-indeno[3xe2x80x2,2xe2x80x2:3,4]naphtho[1,2-b]pyran;
(b) 3,3-di(4-methoxyphenyl)-9-phenyl-3H-9H-indeno[3xe2x80x2,2xe2x80x2:3,4]naphtho[1,2-b]pyran;
(c) 3-(4-methoxyphenyl)-3,9-diphenyl-3H-9H-indeno[3xe2x80x2,2xe2x80x2:3,4]naphtho[1,2-b]pyran;
(d) 3-(4-morpholinophenyl)-3,9-diphenyl-3H-9H-indeno[3xe2x80x2,2xe2x80x2:3,4]naphtho[1,2-b]pyran;
(e) 3,3-di(4-methoxyphenyl)-9-(3-methoxyphenyl)-11-methoxy-3H-9H-indeno[3xe2x80x2,2xe2x80x2:3,4]naphtho[1,2-b]pyran;
(f) 3-(4-methoxyphenyl)-3-phenyl-9-(3-methoxyphenyl)-11-methoxy-3H-9H-indeno[3xe2x80x2,2xe2x80x2:3,4]naphtho[1,2-b]pyran;
(g) 3-(4-methoxyphenyl)-3-phenyl-9-methyl-11-methoxy-9-(3-methoxyphenyl)-3H-9H-indeno[3xe2x80x2,2xe2x80x2:3,4]naphtho[1,2-b]pyran;
(h) 3,3-di(4-methoxyphenyl)-9-methyl-11-methoxy-9-(3-methoxyphenyl)-3H-9H-indeno[3xe2x80x2,2xe2x80x2:3,4]naphtho[1,2-b]pyran;
(i) 3,3-di(4-methoxyphenyl)-9-methyl-11-methoxy-3H-9H-indeno[3xe2x80x2,2xe2x80x2:3,4]naphtho[1,2-b]pyran;
(j) 3,3-di(4-methoxyphenyl)-9,9-dimethyl-11-methoxy-3H-9H-indeno[3xe2x80x2,2xe2x80x2:3,4]naphtho[1,2-b]pyran;
(k) 3-(4-methoxyphenyl)-3-phenyl-9,9-dimethyl-11-methoxy-3H-9H-indeno[3xe2x80x2,2xe2x80x2:3,4]naphtho[1,2-b]pyran;
(l) 3,3-di(4-methoxyphenyl)-9,9-dimethyl-7,11-dimethoxy-3H-9H-indeno[3xe2x80x2,2xe2x80x2:3,4]naphtho[1,2-b]pyran;
(m) 3-(4-methoxyphenyl)-3-phenyl-9,9-dimethyl-7,11-dimethoxy-3H-9H-indeno[3xe2x80x2,2xe2x80x2:3,4]naptho[1,2-b]pyran;
(n) 3-(4-morpholinophenyl)-3-phenyl-9,9-dimethyl-7,11-dimethoxy-3H-9H-indeno[3xe2x80x2,2xe2x80x2:3,4]naphtho[1,2-b]pyran;
(o) 3,3-di(4-methoxyphenyl)-9-methyl-11,13-dimethoxy-3H-9H-indeno[3xe2x80x2,2xe2x80x2:3,4]naphtho[1,2-b]pyran;
(p) 3-(4-methoxyphenyl)-3-phenyl-9-methyl-11,13-dimethoxy-3H-9H-indeno[3xe2x80x2,2xe2x80x2:3,4]naphtho[1,2-b]pyran;
(q) 3-(4-methoxyphenyl)-3-phenyl-9,9-dimethyl-3H-9H-benzo[4xe2x80x3,5xe2x80x3]indeno[3xe2x80x2,2xe2x80x2:3,4]naphtho[1,2-b]pyran; and
(r) 3,3-di(4-methoxyphenyl-9,9-dimethyl-11-fluoro-3H-9H-indeno[3xe2x80x2,2xe2x80x2:3,4]naphtho[1,2-b]pyran.
It is contemplated that the photochromic indenonaphthopyrans of the present invention may each be used alone or in combination with other indenonaphthopyrans of the present invention. Alternatively, the photochromic indenonaphthopyrans of the present invention may be used in combination with one or more other appropriate complementary organic photochromic materials, i.e., organic photochromic compounds having at least one activated absorption maxima within the range of between 400 and 700 nanometers, or substances containing the same. The photochromic compounds may be incorporated, e.g. dissolved or dispersed, in a polymeric organic host material used to prepare photochromic articles which color when activated to an appropriate hue. The complementary organic photochromic materials may include indenonaphthopyrans, naphthopyrans, benzopyrans, phenanthropyrans, spiro(benzindoline)naphthopyrans, spiro(indoline)benzopyrans, spiro(indoline)naphthopyrans, spiro(indoline)quinopyrans, spiro(indoline)pyrans, spiro(indoline)naphthoxazines, spiro(indoline)pyridobenzoxazines, spiro(benzindoline)pyridobenzoxazines, spiro(benzindoline)naphthoxazines, spiro(indoline)benzoxazines, organo-metaldithizonates, e.g. mercury dithizonates, fulgides, fulgimides and mixtures of such photochromic compounds. Such photochromic compounds are described in U.S. Pat. Nos. 5,645,767 and 6,153,126.
The photochromic compounds of the present invention may be associated with a polymeric organic host material or other substrate by various means. They may be incorporated, i.e., dissolved and/or dispersed, into the host material, polymerized with other components of the host material, and/or incorporated into a coating applied to a substrate, e.g., a polymeric coating applied to one surface of the polymeric organic host material.
Each of the photochromic substances described herein may be used in amounts (or in a ratio) such that an organic host material or substrate to which the photochromic compounds or mixture of compounds is associated, exhibits a desired resultant color, e.g., a substantially neutral color when activated with unfiltered sunlight, i.e., as near a neutral color as possible given the colors of the activated photochromic compounds. Neutral gray and neutral brown colors are preferred. Further discussion of neutral colors and ways to describe colors may be found in U.S. Pat. No. 5,645,767 column 12, line 66 to column 13, line 19.
The amount of the photochromic indenonaphthopyrans to be applied to or incorporated into a coating composition or host material is not critical provided that a sufficient amount is used to produce a photochromic effect discernible to the naked eye upon activation. Generally such amount can be described as a photochromic amount. The particular amount used depends often upon the intensity of color desired upon irradiation thereof and upon the method used to incorporate or apply the photochromic compounds. Typically, the more photochromic compound applied or incorporated, the greater is the color intensity up to a certain limit.
The relative amounts of the aforesaid photochromic compounds used will vary and depend in part upon the relative intensities of the color of the activated species of such compounds, the ultimate color desired and the method of application to the host material or substrate. Generally, the amount of total photochromic compound incorporated into or applied to a photochromic optical host material may range from 0.05 to 2.0, e.g., from 0.2 to 1.0, milligrams per square centimeter of surface to which the photochromic compound is incorporated or applied. The amount of photochromic material incorporated into a coating composition may range from 0.1 to 40 weight percent based on the weight of the liquid coating composition.
The photochromic indenonaphthopyrans of the present invention may be associated with the host material by various methods described in the art. See, for example, column 13, lines 40 to 58 of U.S. Pat. No. 5,645,767. Aqueous or organic solutions or dispersions of the photochromic compounds may be used to incorporate the photochromic compounds into a polymeric organic host material or other materials such as textiles and coating compositions. Coating compositions may be applied to the substrate using a coating process such as that described in U.S. Pat. Nos. 3,971,872, 6,025,026 and 6,150,430.
Application of the polymeric coating may be by any of the methods used in coating technology such as, for example, spray coating, spin coating, spread coating, curtain coating, dip coating, casting or roll-coating and methods used in preparing overlays, such as the method of the type described in U.S. Pat. No. 4,873,029. The application method selected also depends on the thickness of the cured coating. Coatings having a thickness ranging from 1 to 50 microns may be applied by conventional methods used in coating technology. Coatings of a thickness greater than 50 microns may require molding methods typically used for overlays.
The polymeric coating composition includes compositions resulting in thermoplastic or thermosetting coatings, which are described in the Kirk-Othmer Encyclopedia of Chemical Technology, Fourth Edition, Volume 6, pages 669 to 760. The coating may comprise at least one polymer selected from the group consisting of polyurethanes, melamine resins, polyvinyl alcohol, polyacrylates, polymethacrylates, polyamide resins and epoxy resins. Such polymer-forming coating compositions are described in U.S. Pat. No. 4,425,403.
The host material will usually be transparent, but may be translucent or even opaque. The host material need only be pervious to that portion of the electromagnetic spectrum, which activates the photochromic substance, i.e., that wavelength of ultraviolet (UV) light that produces the open or colored form of the substance and that portion of the visible spectrum that includes the absorption maximum wavelength of the substance in its UV activated form, i.e., the open form. Preferably, the host color should not be such that it masks the color of the activated form of the photochromic compounds, i.e., so the change in color is readily apparent to the observer. Compatible tints may be applied to the host material as described in U.S. Pat. No. 5,645,767 in column 13, line 59 to column 14, line 3.
Most preferably, the polymeric organic host material is a solid transparent or optically clear material, e.g., materials suitable for optical applications, such as plano, ophthalmic and contact lenses, windows, automotive transparencies, e.g., windshields, aircraft transparencies, plastic sheeting, polymeric films, etc.
Examples of polymeric organic host materials which may be used with the photochromic compounds described herein include: polymers, i.e., homopolymers and copolymers, of the bis(allyl carbonate) monomers, diethylene glycol dimethacrylate monomers, diisopropenyl benzene monomers, ethoxylated bisphenol A dimethacrylate monomers, ethylene glycol bismethacrylate monomers, poly(ethylene glycol) bismethacrylate monomers, ethoxylated phenol bismethacrylate monomers, alkoxylated polyhydric alcohol acrylate monomers, such as ethoxylated trimethylol propane triacrylate monomers, urethane acrylate monomers, such as those described in U.S. Pat. No. 5,373,033, and vinylbenzene monomers, such as those described in U.S. Pat. No. 5,475,074 and styrene; polymers, i.e., homopolymers and copolymers, mono- or polyfunctional, e.g., di- or multi-functional, acrylate and/or methacrylate monomers, poly(C1-C12 alkyl methacrylates), such as poly(methyl methacrylate), poly(oxyalkylene)dimethacrylate, poly(alkoxylated phenol methacrylates), cellulose acetate, cellulose triacetate, cellulose acetate propionate, cellulose acetate butyrate, poly(vinyl acetate), poly(vinyl alcohol), poly(vinyl chloride), poly(vinylidene chloride), polyurethanes, polythiourethanes, thermoplastic polycarbonates, polyesters, poly(ethylene terephthalate), polystyrene, poly(alpha methylstyrene), copoly(styrene-methyl methacrylate), copoly(styrene-acrylonitrile), polyvinylbutyral and polymers, i.e., homopolymers and copolymers, of diallylidene pentaerythritol, particularly copolymers with polyol (allyl carbonate) monomers, e.g., diethylene glycol bis(allyl carbonate), and acrylate monomers, e.g., ethyl acrylate, butyl acrylate. Further examples of polymeric organic host materials are disclosed in the U.S. Pat. No. 5,753,146, column 8, line 62 to column 10, line 34.
Transparent copolymers and blends of transparent polymers are also suitable as host materials. Preferably, the host material or substrate for the photochromic polymeric coating composition is an optically clear polymerized organic material prepared from a thermoplastic polycarbonate resin, such as the carbonate-linked resin derived from bisphenol A and phosgene, which is sold under the trademark, LEXAN; a polyester, such as the material sold under the trademark, MYLAR; a poly(methyl methacrylate), such as the material sold under the trademark, PLEXIGLAS; polymerizates of a polyol(allyl carbonate) monomer, especially diethylene glycol bis(allyl carbonate), which monomer is sold under the trademark CR-39, and polymerizates of copolymers of a polyol (allyl carbonate), e.g., diethylene glycol bis(allyl carbonate), with other copolymerizable monomeric materials, such as copolymers with vinyl acetate, e.g., copolymers of from 80-90 percent diethylene glycol bis(allyl carbonate) and 10-20 percent vinyl acetate, particularly 80-85 percent of the bis(allyl carbonate) and 15-20 percent vinyl acetate, and copolymers with a polyurethane having terminal diacrylate functionality, as described in U.S. Pat. Nos. 4,360,653 and 4,994,208; and copolymers with aliphatic urethanes, the terminal portion of which contain allyl or acrylyl functional groups, as described in U.S. Pat. No. 5,200,483; poly(vinyl acetate), polyvinylbutyral, polyurethane, polythiourethanes, polymers of members of the group consisting of diethylene glycol dimethacrylate monomers, diisopropenyl benzene monomers, ethoxylated bisphenol A dimethacrylate monomers, ethylene glycol bismethacrylate monomers, poly(ethylene glycol) bismethacrylate monomers, ethoxylated phenol bismethacrylate monomers and ethoxylated trimethylol propane triacrylate monomers; cellulose acetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, polystyrene and copolymers of styrene with methyl methacrylate, vinyl acetate and acrylonitrile.
More particularly contemplated is use of the photochromic indenonaphthopyrans of the present invention with optical organic resin monomers used to produce optically clear coatings and polymerizates, i.e., materials suitable for optical applications, such as for example plano and ophthalmic lenses, windows, and automotive transparencies. Such optically clear polymerizates may have a refractive index that may range from 1.48 to 1.75, e.g., from 1.495 to 1.66.
Specifically contemplated are polymerizates of optical resins sold by PPG Industries, Inc. under the CR-designation, e.g., CR-307, CR-407 and CR-607, and polymerizates prepared for use as hard or soft contact lenses. Methods for producing both types of contact lenses are disclosed in U.S. Pat. No. 5,166,345, column 11, line 52, to column 12, line 52. Additional polymerizates contemplated for use with the photochromic naphthopyrans of the present invention are polymerizates used to form soft contact lenses with high moisture content described in U.S. Pat. No. 5,965,630 and extended wear contact lenses described in U.S. Pat. No. 5,965,631.
The present invention is more particularly described in the following examples, which are intended as illustrative only, since numerous modifications and variations therein will be apparent to those skilled in the art.